Accurate equilibrium structures for small polyatomic molecules, radicals and carbenes

Abstract

The paper reports on recent efforts to establish accurate equilibrium structures for small polyatomic molecules, radicals and carbenes most of which are of relevance to interstellar cloud chemistry, combustion processes or atmospheric chemistry. Among these are the well–known interstellar cyanopolyynes HC3N and HC5N, members of the series NC2 n N, HC2 n + 1P and NC2 n P, linear silicon carbides of type SiC2 n and pure carbon chains up to C14, the radicals HC3O, HOCO and CH2CHO as well as cumulene carbenes of type H2C n . Whenever possible, a mixed experimental/theoretical procedure is employed which makes use of accurate experimental values for the ground–state rotational constants of a sufficiently large number of different isotopomers plus the results of coupled cluster calculations (variant CCSD(T)). In less favourable cases, the transfer of well–established correction parameters as developed from related smaller molecules appears to be the method of choice.